1. Technical Field
The present invention relates to a symmetrically substituted cationic monomer, a cationic polyelectrolyte synthesized from the symmetrically substituted cationic monomer, a pH-responsive cationic polyacid synthesized from the cationic polyelectrolyte, a polyzwitterionic acid synthesized from the cationic polyacid, a polyzwitterion/anion and polyzwitterion/dianon synthesized from the polyzwitterionic acid, and the corresponding methods by which each compound and polymer is formed and use of the polyzwitterionic acid as an antiscalant.
2. Description of the Related Art
The “background” description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present invention.
Phosphorus, one of the essential elements required for life on earth, is observed in biology in the form of a phosphate or a pyrophosphate which is a required component of DNA, RNA, phospholipids and adenosine triphosphate (ATP). Phosphonates on the other hand are less common in nature (Horiguchi, M.; Kandatsu, M. Nature 1959, 184, 901; K. D. Demadis In Progress in Solid State Chemistry Research, Buckley, R. W. Ed.; 2007 Nova Science Publishers, Inc.; ISBN 1-60021-567-X; pp. 109-172—each incorporated herein by reference in its entirety); however, numerous synthetic organic phosphonates phosphonates have found widespread use in various industries (Ternan, N. G.; Mc Grath, J. W.; Mc Mullan, G.; Quinn, J. P. World J. Microb. Biot. 1998, 14, 635—incorporated herein by reference in its entirety). Phosphonates have been used to chelate divalent cations such as Ca2+ and Ba2+ ions (Nowack, B. Water Res. 2003, 37, 25331; Thatcher, G. R. J.; Campbell, A. S. J. Org. Chem. 1993, 58, 2272—each incorporated herein by reference in its entirety) in water softening, detergents, textile industry as well as to inhibit the deposition of scale. Polymers containing both amine and phosphonic acid groups are used as chelating resins for metal ions (Alexandratos, S. D.; Hong, M. J. Sep. Sci. Technol. 2002, 37, 2587; Eiffler, J.; Joeken, G.; Schneider, H. P., Invs; The Dow Chemical Co., U.S. Pat. No. 5,109,074, Apr. 28, 1992; Alfano, N. J.; Shenberger, D. M., Invs; Calgon Co., U.S. Pat. No. 5,454,954, Oct. 3, 1995; Sato, Y.; Murayama, K.; Nakai, Y., Invs; General Agency of Industrial Science and Technology, U.S. Pat. No. 5,212,207, May 18, 1993; Riedelsberger, K.; Jaeger, W. Des. Mon. Polym. 1998, 1, 387). Butler's cyclopolymerization protocol (Butler, G. B. Cyclopolymerization and Cyclocopolymerization; Marcel Dekker: New York, 1992; Kudaibergenov, S.; Jaeger, W.; Laschewsky, A. Advances in Polymer Science 2006, 201, 157; Singh, P. K.; Singh, V. K.; M. Singh, e-Polymers 2007, 030, 1; Jaeger, W.; Bohrisch, J.; Laschewsky, A. Prog. Polym. Sci. 2010, 35, 511—each incorporated herein by reference in its entirety) using diallylamine salts bearing aminomethylphosphonate motif has been utilized in the synthesis of cross-linked polyphosphonate resins which are found to be very effective in the removal of toxic metal ions (Al Hamouz O. C. S.; Ali, S. A. Ind. Eng. Chem. Res. 2012, 51, 14178; Al Hamouz, 0. C. S.; Ali, S. A. Sep. Purific. Technol. 2012, 98, 94—each incorporated herein by reference in its entirety).
The area of applications also includes ion exchangers (Ortiz-Avila, C. Y.; Bhardwaj, C.; Clearfield, A. Inorg. Chem. 1994, 33, 2499—incorporated herein by reference in its entirety), nonlinear optics (Petruska, M. A.; Watson, B. C.; Meisel, M. W.; Talham, D. R. Chem. Mater. 2002, 14, 2011; Cao, G.; Hong, H. G.; Thompson, M. E. Acc. Chem. Res. 1992, 25, 420; Fu, R.; Zhang, H.; Wang, L.; Hu, S.; Li, Y.; Huang, X.; Wu, X. Eur. J. Inorg. Chem. 2005, 3211—each incorporated herein by reference in its entirety), catalysts (Benitez, I. O.; Bujoli, B.; Camus, L. J.; Lee, C. M.; Odobel, F. Talham, D. R. J. Am. Chem. Soc. 2002, 124, 4363—incorporated herein by reference in its entirety), and molecular sensors (Brousseau III, L. C.; Aurentz, D. J.; Benesi, A. J.; Mallouk, T. E. Anal. Chem. 1997, 69, 688—incorporated herein by reference in its entirety). A novel sulfonated poly(ether ether ketone)/phosphonated polysulfone polymer blends for proton conducting membranes was recently reported (Abu-Thabit, N. Y.; Ali, S. A.; Zaidi, S. M. J.; Mezghani, K. J. mater. Res. 2012, 27 1958—incorporated herein by reference in its entirety). Cyclopolymers bearing aminopropylphosphonate motif have been synthesized and evaluated as antiscalants (Kazi, I. W.; Rahman, F.; Ali, S. A. Polym. Engg. Sci.: DOI 10.1002/pen.23548; Ali, S. A.; Kazi, I. W.; Rahman F. Polym. Int. DOI 10.1002/pi.4539—each incorporated herein by reference in its entirety) and as a polymer component in the construction of aqueous two-phase systems (Al-Hamouz, O. C. S.; Ali, S. A. J. Chem. Eng. Data 2013, 58, 1407—incorporated herein by reference in its entirety). Some phosphonates are used as medicines: the antiretroviral drug Tenofovir is used in the treatment of viral diseases such as HIV and hepatitis B (De Clercq, E. Annu. Rev. Pharmacol. Toxicol. 2011, 51, 1. —incorporated herein by reference in its entirety). Aminophosphonic acids are structural analogues of amino acids and as such suitable for various biological applications (Kafarski, P.; Lejczak, B. Phosphorus Sulfur Silicon 1991, 63, 193—incorporated herein by reference in its entirety). Two recent reports describe the polymerizations of phosphonated-bis(methacrylamide)s for dental applications (Akgun, B.; Savci, E.; Avci, D. J. Polym. Sci. Part A: Polym. Chem. 2012, 50, 801; Bilgici, Z. S.; Ordu, O. D.; Isik, M.; Avci, D. J. Polym. Sci. Part A: Polym. Chem. 2011, 49, 5042—each incorporated herein by reference in its entirety). Generally, polyphosphonates are used as flame retardants (Lu, S. Y.; Hamerton, I. Prog. Polym. Sci. 2002, 27, 1661—incorporated herein by reference in its entirety), in the biomedical field as adhesion promoters to dental tissue (Moszner, N.; Salz, U.; Zimmermann, J. Dent. Mater. 2005, 21, 895; Xu, X.; Wang, R.; Ling. L.; Burgess, J. O. J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 99—each incorporated herein by reference in its entirety) and bone (Erez, R.; Ebner, S.; Attali, B.; Shabat, D. Bioorg. Med. Chem. Lett. 2008, 18, 816; Alferiev, I.; Vyavahare, N.; Song, C.; Connolly, J.; Hinson, J. T.; Lu, Z.; Tallapragada, S.; Bianco, R.; Levy, R. Biomaterials 2001, 22, 2683; Wang, L.; Zhang, M.; Yang, Z.; Xu, B. Chem. Commun. 2006, 2795—each incorporated herein by reference in its entirety). pH-responsive bisphosphonates R1R2C(PO3H)2, analogs of pyrophosphates O(PO3H)2, are used as corrosion inhibitors (Gunasekaran, G.; Natarajan, R.; Muralidharan, V. S.; Rao, B. V. A. Anti-Corros. Method. M. 1997, 44, 248—incorporated herein by reference in its entirety) in concrete, coatings, rubber blends, etc, and complexing agents in oil industries (Graham, R.; Russell, G. Bone 2011, 49, 2—incorporated herein by reference in its entirety), as antiscalants to sequester calcium ions, and as inhibitors of bone resorption in bone-related diseases (Fleish, H.; Neuman, W. F. Am. J. Physiol. 1961, 1296—incorporated herein by reference in its entirety).
pH-responsive polyphosphonates bearing nitrogen such as protonated (NH+) aminomethyl—and aminopropylphosphonate residues have been synthesized using a cyclopolymerization technique (Al-Hamouz, O. C. S.; Ali, S. A. J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 3580; Ali S. A.; Al-Hamouz, O. C. S. Polymer 2012, 53, 3368; Ali, S. A.; Abu-Thabit, N. Y.; Al-Muallem, H. A. J. Polym. Sc., Part A: Polym. Chem. 2010, 48, 5693; Abu-Thabit, N. Y.; Kazi, I. W.; Al-Muallem, H. A.; Ali, S. A. Eur. Polym. J. 2011, 47, 1113—each incorporated herein by reference in its entirety). The cylopolymerization of a diallyl quaternary amine salt [CH2═CH—CH2)2NH+CH(PO3H)(PO3−)] having bisphosphonate functionality with the P attached to the same carbon has been reported (see Riedelsberger above). Cyclopolymerization of a symmetric bisphosphonate diallyl quaternary ammonium salt having phosphorous atoms attached two different carbons has not yet been reported. Keeping in view the importance of phosphonates, herein the synthesis and cyclopolymerization of a new bisphosphonate monomer 4 bearing bis-3-phosphorylpropyl substituents is reported (see Scheme 1 herein). Ester hydrolysis of cyclopolymer 5 to pH-responsive 6 permits examination of solution properties, determination of acid dissociation constants and efficiency as an antiscalant to inhibit CaSO4 scale formation in desalination plants.